Lubricating composition



Patented Dec. 2, 1941 i UNITED STATES PATENT OFFlCE LUBRICATING COMPOSITION Bert H. Lincoln and Gordon D. Byrkit, Ponea City, kla. assignors, by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland, Ohio, a corporation of Delaware No Drawing.

9 Claims.

vide a lubricating composition having the aboveadvantage which also will have a relatively low DOur point, good color and stability, and which may be manufactured at small expense.

Other objects of this invention will appear as the description proceeds.

Application October 12, 1939, Serial No. 299,186

Our invention, then, consists of the -means hereinafter fully described and particularly pointed out, in the claims, the following description setting forth in detail certain means embodying the invention, such disclosed means constituting, however, but'some of the various ways in which the principle of the invention may be used.

Broadly stated, this invention comprises the provision of a lubricating composition including therein a minor amount of halogen-bearing foots oil.

Halogenated ,or, more specifically, chlorinated, foots oil is stable to heat, light and long standing and is of a sufiiciently light color that when blended with a lubricating oil it is unobjection- 1 able to the retailer.

, oil is chlorinated a. homogeneous product is pro- Furthermore, when foots duced which does not require further treatment before it is ready for use. This is of particular advantage inasmuch as minor amounts, if left unchlorinated, would tend to elevate the pour point of the finished lubricant and, on the other hand, if a portion of the addition agent were too highly chlorinated it might tend to become unstable.

encountered with certain other fractions of hydrocarbon oils these properties ,of foots oil were entirely unexpected and led to further experi- 'mentation to determine whether its other properties were such as to render it a desirable extreme pressure addition agent.

oil and the waxes, it has been recognized as a petroleum fraction unlike all others. In practical refinery operation, it is removed with the wax from the raw wax distillate fraction for the When foots oil is employed a uniformproduct is obtained. In view of the difllculties Likewise, it may not bein- Since it has chemical production of a satisfactory lubricating oil, the separation usually being accomplished by pressing. The foots oil is subsequently removed from the wax for the production of a commercially salable wax. The term "foots oil as used in this patent shall include the hydrocarbon fraction that is removed from petroleum in manufacturing petroleum wax and high grade lubricating stocks, said fraction having physical and chemical properties different from wax and neutral oil. The wax-foots oil separation is usually accomplished by sweating. Further proof of the fact that foots oil is unlike lubricating oil and unlike Wax is obvious from the universal practice of using foots oil for the production of'gasoline by thermal or catalytic cracking. I The foots oil employed in this invention may be refined or may be satisfactorily used as derived from petroleum processing. The refining may be accomplished by simple filtering, solvent extracting, clay contacting, clay percolation, sulfuric acid treatment, or any combination of these and other common refining processes. Very small amounts of sulfuric acid have been found sufficient for effective treatment of foots oil; for example, four to ten pounds of 98 Baum acid per barrel of foots oil followed by clay contacting for neutralization gives a very satisfactory product.

The raw or refined foots oil may be chlorinated by the usual methods, and amounts of chlorine over a wide range may be used up to 60% and more. In the lower ranges, of from 10 to 25 per cent chlorine, a large proportion of the chlorine is in relatively active form. In higher ranges, for

, by a combination of these and other processes which are not critical so long as uncombined chlorine or hydrogen chloride is removed.

The chlorinated foots oil may be further improved for certain uses by treatments which will remove the least stable part of the chlorine, for example by treatment with alkalies, aluminum chloride, inorganic sulphides, metallic xanthates, etc.

There'follows one theory which may serve to explain the reason for the unexpected advantages of halogenated footsoil over other halo genated materials which have been proposed for the purpose. It is to be understood that this invention is not to be considered as limited in any way by such explanation.

The process of obtaining foots oil may be considered a double fractionation in that the chilling and pressing operations separate lubrieating hydrocarbons from the foots oil and wax hydrocarbons. The subsequent sweating operation is likewise a fractionation for the same reason, accomplishing the separation of the wax hydrocarbons from the foots oil hydrocarbons. The foots oil is thus atwice fractionated product obtained by processes different from those applied to any other petroleum fraction. We be-' lieve that the special properties of foots oil are due in part to these peculiar fractionations whereby it is obtained. No other product of petroleum has been subjected to this particular combination of processes; therefore no other .product has its particular properties. It is possible that these fractionations serve to segregrate in the foots oil some special group of hyparticularly such lubricants which contain sulfur-bearing materials. The preparation of the chlorinated foots oil has been described above, and we may use up to 40 per cent or more of chlorine in the foots oil. The quantity of chlorinated foots oil in the finished blend may vary from 0.5% to 2.0% up to or per cent or more so that the chlorine content of the blend from this source may be as much as 5% or even 10% or more.

The sulfur-bearing materials which we may use in accordance with our invention may be compounds of well-known constitution or the relatively imperfectly known sulfurized materials obtained by heating various substances or mixtures with sulfur or sulfur compounds such as sulfur chloride, sulfuryl chloride, thionyl chloride, phosphorus trisulfide, phosphorus pentasulfide, inorganic sulphides and polysulphides, xanthates, and the like. The blends of chlorinated foots oil with these sulfurized products in oils of lubricating viscosity appear to be more suitable for violent extreme pressure use and for use with the soft alloy bearings such as cadmium-silver and copper lead and other alloys having the corrosion characteristics of this group than blends with most of the compounds of definitely known constitution. The reason for this is obscure, but it is possible that the sulfurized materials contain sulfur in the degree of stability most suited for corrosion prevention when activated by our chlorinated foots oil whereas the sulfur-in the compounds of more definitely known constitution is too stable. Regardless of this discussion of the causes, the empirical fact remains that the improved results we obtained with our chlorinated foots oil are especially pronounced with the sulfurized compounds. on the other hand, it is to be under- 7 stood that, for particular applications, blends with stable sulfur compounds of definitely known constitution are advantageously used. The amount of sulfur in the finished blend may vary widely depending upon the form in and the purpose for which the sulfur is added. In crankcase lubricants amounts of sulphur as low as .0l% or less may be used with advantageous results, less than .05% of sulfur being usually sufiicient. For gear lubricants there may be from .10% up to 10% or more of sulfur in the finished composition. Up to 20% or more of sulfur may advantageously be present in cutting oils. For the purpose of inhibiting corrosion of the sensitive bearing alloys having the corrosion characteristics of cadmium-silver, copper-lead, and the like, we prefer to use such amounts of compounds as give up to 0.5% of sulfur in the finished blend.

The combination of halogenated foots oil with sulfur-bearing materials in lubricants has certain advantages in film strength and oiliness over either when used alone. This advantage is not cumulative but is due to the combination. In what manner this combination of halogenated foots oil and sulfur-bearing materials attains this advantage is not fully understood. In the so-called violent extreme pressure lubricants now required for some automotive uses, such as for hypoid gears, halogen compounds used alone or sulfur-bearing materials used alone are insuflicient; but the combination is satisfactory, The use of blends containing our halogenated foots oil and sulfur-bearing materials are of outstanding suitability for such purposes.

In the manufacture of such violent extreme pressure lubricants, we may use sulfurized compounds with our halogenated foots oil or sulfur compounds of known constitution. Particularly suited for such purposes are the sulfur-bearing materials containingactive sulfur as contrasted with those containing only inactive sulfur. By active sulfur we mean that form which is present when a 10% blend of the sulfur-bearing material with of gasoline, kerosene, or a lubricating oil (itself free of active sulfur according to this test) will appreciably discolor a bright copper strip immersed therein and held at 210 F. for 30 minutes. If the copper strip is not appreciably discolored, all the sulfur present is in the inactive form. Compounds containing only in active sulfur may be satisfactorily employed in the manufacture of extreme pressure lubricants.

Sulfurized materials containing active and inactive sulfur may be manufactured as desired from any unsaturated material according to the modification of conditions used. In general, materials containing active sulfur may be obtained by the use of free sulfur as sulfurizing reagent, large proportions of reagent, lowest possible temperatures, short times of heating, absence of unreactive diluents, little or no refining, and operating at atmospheric or lower pressures. Products containing only inactive sulfur are more likely to be obtained-by the use as sulfurizing reagents of sulfur compounds such as phosphorus trisulfide in place of sulfur, relatively small proportions of reagent, higher temperatures, longer times of heating, use of diluents, thorough refining, and operation at superatmospheric pressures.

It is frequently desirable in these violent extreme pressure gear lubricants to have large amounts of chlorine present in the blends for best results. In such cases, we use a relatively highly chlorinated foots oil and relatively large amounts of it in the blend.

Some of the sulfur-bearing materials we may use in the blends with our halogenated foots oil are: amyl sulfide, amyl disulfide, amyl polysulfide, amyl sulfoxide, amyl sulfone, benzyl sulfide, benzyl disulfide, chlorobenzyl disulfide, paracresyl ethyl thioether, beta, beta prime-dihydroxyethyl sulfide, diphenyl sulfide, diphenylthiocarbazide, diphenylthiourea, dithiodiglycol, ethyl dithiooxalate, ethyl thiocyanate, ethylene thiocyanate, thiocresol, thiostearic acid, thiophenylacetone, trithioacetone, ethionic acid and its esters, is ethlonic acid and its esters, phenyl mercaptostearate, thiobenzamide, thioacetanilide, benzyl sulfate, benzyl sulfite, trithiane, dithiane, thianthrene,

chlorostearate, chlorodiphenylene oxide, and the like.

Our addends are admirably adapted for use in lubricating oils of all types, including those designed for use in automotive crankcases, Diesel oils, and any other oils of lubricating viscosity. Furthermore, our addends'are advantageously blended in gasoline and other petroleum fuels either directly or'after being blended first in a lubricating oil and then added to the fuel. Soapthickened mineral oils of all types ranging from those showing only a slight increase in viscosity chlorothianthrene, methyl amylxanthate, butyl iurized polymers from gray towers, sulfurized pe-- troleum residues, sulfurized octadecene, and the like.

The sulfur-bearing material may be introduced into the composition in the form of a sulfurbearing substituent for the more reactive part of the halogen in the halogenated foots oil. For example, chlorinated foots oil which contains relatively reactive chlorine may be treated with sulfur-bearing reagents such as inorganic hydrosulfides, sulfides, polysulfides, xanthates, and the like, so that the more reactive part of the chlorine present in the chlorinated foots oil will be replaced by the hydrosulfide, sulfide, polysulfide, xanthate, etc.,' radical. The resultant composition when added to mineral oil will then provide both the sulfur bearing material anda stabilized form of chlorinated foots oil.

By oil of lubricating viscosity in the appended over that of the mineral oil alone to.the semisolid and solid greases containing fifty per cent or more of soap are amenable to treatment ac- In making these cording to our invention. greases, the usual soaps such as sodium stearate, aluminum stearate, calcium soaps of beta fat, and the like, may be used. Various other thickening ingredients or materials for other purposes may be added. These include yarn, hair, graphite, glycerol, water, lampblack, mica, zinc dust, litharge, and the like.

Lubricating gasolines may be prepared by blending one per cent'or less of any of the appended examples of lubricants in a petroleum fuel. It is to be understood that the hydrocarbon oil in the treated fuels may be of a viscosity of. from about 35 second at 100 RS. S. U. to 350 seconds or more, and the amount-of oil blended with our combination of addends may vary between 0 and 99.5 percent. In some cases the fuel may be prepared without adding any hydrocarbon oil.

In practice, it is better to employ in conjunction with our chlorinated foots oil such sulfur compounds as have boiling points over 225 in order that the added sulfur compound may not be evaporated or distilled out during use. The

selection of a particular compound or compounds to be used is to be made considering the physical and chemical properties of the variouscompounds and the use to which the blend is to be claims, we mean to include the so-called mineral of hydrocarbon oils and also vegetable, animal, voltolized, synthetic or synthetically treated oils. We include aluminum chloride treated oils, mercury treated oils, sulfurized oils, distilled and residual oils, and the like, in some of our blends. These oils may be used alone or blended with each other in our compositions.

Furthermore, we are not limited to the use of any onesulfur compound in my blends; but mixtures of twoor more sulfur-bearing compounds may sometimes be used advantageously. In mak- Eng these blends, we may mix the addends together first and then add themto the oil, or we may combine one addend with the oil, blend in the second, and. so on until the composition is complete.

It is frequently advantageous to add to our blends containing sulfur-bearing materials and our chlorinated foots oil such other products as improve the final blends. Some of these second-- ary addends are pour test depressors such as a naphthalene-chlorinated wax condensation product, oxidation'inhibitors such as tri-p-tert-butylphenyl phosphite and dicyclohexylamine. Other such auxiliary addends which may be used arecalcium dichlorostearate, triethyltin cetyl 3- put. Thus, if water is likely to be present during use, a compound or combination of compounds is selected which is not aifected by water.

If a particular added compound proves too volatile for its application, a higher boiling material should be used and the more volatile compound used for blending in an oil intended for duty at lower temperatures. In general, for automotive crankcase lubricants, we prefer to use compounds having vapor pressures of less than atmospheric at 250 F.

. Example 1 Per cent Chlorinated foots oil (22 per cent Cl) 3.5 Benzyl disulfide 1.5 Mid-Continent base SAE 30 95.0

Example 3 Chlorinated foots oil (22 per cent 01) 2s sulfurized methyl linoleate 11.3 per cent S) 1.3

Methyl dichlorostearate 0.7 Paraflin base SAE 40 95.5

100.0 I Example 3 p v Chlorinatedfoots oil (12 per cent Cl) 3.0 Naphtha xanthate 1.0 Steam refined stock 88.0 Raw '70 pale neutral 8.0

Example 4 Example 13 Per cent Per cent Chlorinated foots oil (12 per cent C1) 1.2 Chlorinated footsoil (22% chlorine) 10.0 Triethyltin salt of sulfurized linoleic acid 0.5 Sulfur 1.0 Chlorodiphenylene oxide 1.0 5 Neutral oil 220 viscosity at 100 F. S. S. U. 89.0 Naphthalene-chlor wax condensation product 0.5 100.0 Neutral oil -J. 40.5 Example 14 Bright Stock 10 Chlorinated foots oil (40% c1) 8.0

Mineral lubricating oil (84 seconds at loo- 210 F.) 92.0 Example Sulfurized pine oil 2.0 100.0 Chlorinated foots oil (28 per cent Cl) Example 5 Vmtonzed com on "i5 2"; Chlorinated foots oil (40 01) s 0 A a California naphthemc base E I nibenzyl disulphide u 2.5

0 Mineral lubricating oil (84 seconds at Example 6 2 F.) 89.5

" Chlorinated foots oil (28 per cent 311) 1.1.01-

100.0 ize ar oi 3 1 Example 14 was tested on three well known Lime 12 and conventional types of testing machines and Water 03 the results of such tests, as compared with cor- Dichlorostearic acid 1.1 responding s s n the untreated base oil are as Bright t k 12.2 follows: Distillate (428 seconds at 100 F.) 70.1

Break down load loo-0 so Typc of machine Example 7 gg gfif Example Gasoline 99.50 on Pounds Pounds Chlorinated foots oil (12 per cent C1) el 6 21 Sulfurized methyl linoleate B2 86 a:i oitob'iifi fiM'IIIIIIIIII About 133 iii s. A. E.@i,000 R. P. M About 100 315 100.00 Example 8 The S. A. E. machine was loaded at the rate of 83.5 lbs. per minute. Chlorinated root's (12 3 C1) a The gear lubricant of Example 15 was tested Chlormated zi xan e b on the Almen machine and was found to have s i s t 1 9. film strength in excess of the capacity of the aw p 9 m machine (30 lbs.).

100 0 Example 15 also gave satisfactory results when Ex mp1 6 9 tested in accordance with the axle test described in section 2 of the specifications for hypoid Chlorinatedfoots oil (40 per cent (:1) 1.5 gear l r an s. pu s d y en a Mot rs Sulfurized methyl linoleate(11.3 per cent 3) 1.3 Co ation under the title General Motors m amylxanthylxanthate 0.7 a ds-Know G ar Lubri ants -M Paramn base SAE 0 9 ,5 60 4664M, vol. II, pages D-5 and D-6, dated March v 1939. This composition also met these same 1001 specifications in all other respects; notably the.v Example 10 "active chlorine, determination made according to section 6K of such specifications, was C o ina d OO 0 (17 D cent found to be 2.1% of the total 3.2% of chlorine Sulfurized methyl linoleate (11.3 per cent present in the composition 5 woiltamlne y o Throughout the foregoing description of this Methyl dlchlolosteal'a-te invention reference has been made to lubricating Paramn a SAE 30 compositions which in general comprise a major a o0 proportion of a suitable lubricating oil base to v loo-o which has been added minor amounts of chlo-. Example 11 'rinated foots oil either alone or in combination Chlorinated mots on (17 per cent on 25 with sulfur. It will be observed that a very sat- Sulfurized methyl linoleate (11.3 per cent ismctory lubricant can be prepared by merFly 3) (containing active lf L5 addingfo a'body of halogenated, or more specifi- Steam refined stocknn; 8&0 cally, chlorinated, foots oil, sulfur in the amounts Raw pale neutral and in the character previously specified, i. e. an

v entirely'satisfactory lubricant for certain pur- 100.0 poses can be prepared by the use of two con- Ezample 12 70 stituents, namely halogenated roots oil and sulfur instead of employing in addition the third Chlorinated foots oil (50% chlorine) -0 constituent such as the suitable oil base. Mid-Continent base SAE 30 99- In addition to the previously named constituenta which may be employed in combination 100.0 in the preparation of a finished compounded lubrlcant in accordance with this invention, it will be found desirable for certain purposes to also include in the composition a separate organic oiwgen compound. Such oxygen compoundwill preferably be of the type which has a vapor pressure less than atmospheric at a temperature of 250 F. and will of course be one which is sufficiently oil soluble so that amounts up to, for example, or even may be employed in the composition in the form of 'a true solution or stable form of colloidal suspension. The organic oxygen compound willbe found to improve the composition by contributing to the oiliness of the blend and to also cooperate with the halogenated foots oil and the organic sulfur compound in the production of an extremely highfilm strength. The separate organic oxygen compound may be selected from the classes consisting-of oxygen bearing derivatives of the paraflin, olefin and acetylene series as well as oxygen bearing derivatives of carbon ring type compound. The ketones, esters, ethers, acids, alcohols, hydroxyamines and salts may be used to advantage. Naturally occurring organic oxygen compounds, such as animal, vegetable and mineral oils, will be found particularly useful, as well as the oxidation products of various petrc-' leum fractions. Additional specific examples of organic oxygen compounds which may thus be employed are benzophenone, resorcinol, acetophenone, aromatic fatty acids such as phenyl stearic acid and salicylic acid, methyl salicylate, esters and salts of aromatic fatty acids such as methyl, ethyl, orbutyl phenyl stearate and sodium and calcium phenyl stearate, diphenyl ether, alkylated aromatic ethers, cyclohexanol, aliphatic alcohols of the type represented by lauryl alcohol, aliphatic esters and salts of the type represented by methyl palmitate, methyl stearate, tri-et'hanol-amine, dipropyl ketone, dibutyl ketone, propionic acid, butyric acid, palmitic acid, stearic acid and hydroxystearic acid.

For certain uses it will be found advantageous to employ the halogen derivatives of any of the above mentioned organic oxygen compounds since such derivatives have the combined effect of not only functioning in a cooperative fashion with the remaining constituents of the composition, i. e. the halogenated foots oil or organic sulfur compound or both, but also provide extreme pressure characteristics directly.

It will be understood that certain features and subcombinations may be employed without reference to other features or combinations. This is contemplated by and is within the scope of the claims. It is further obvious that various changes may be made in details within the scope of the claims without departing from the spirit of the invention. It is therefore to be understood that my invention is not to be limited to the details shown and described.

Other modes of applylngthe' principle of our invention may be employed instead of the one explained, change being made as regards the composition and method herein disclosed. provided the ingredients or steps .stated by any of the following claims or the equivalent of suchstated ingredients or steps be employed.

We therefore particularly point out and distinctly claim as our invention:

1. A lubricating composition comprising a major proportion of oil of lubricating viscosity and a minor proportion of halogenated foots oil.

2. A lubricating composition comprising a major proportion of oil of lubricating viscosity and from about 0.1% to about 20% of chlorinated foots oil containing on the order of 10% to about chlorine. I

3. A lubricant comprising in combination a major proportion of oil of lubricating viscosity, a minor proportion of halogenated foots oil, and a minor proportion of a sulfur-bearing organic compound.

4. A lubricant comprising in combination a major proportion of oil of lubricating viscosity, a minor proportion of chlorinated foots oil, and a minor proportion of a sulfur-bearing organic compound.

5. A lubricant comprising in combination an oil of lubricating viscosity, from 0.1 to 20 per cent a minor proportion of a sulfur-bearing organiccompound having a vapor pressure of less than atmospheric at 250 F.

8. A lubricating composition comprising a major proportion of refined mineral lubricating oil to which has been added minor amounts of halogenated foots oil and an organic sulfur compound.

9. A lubricating composition comprising a ma jor proportion of mineral lubricating oil and minor proportions each of halogenated foots oil, an organic sulfur compound and an organic compound, said sulfur and oxygen compounds being of the type having a vapor pressure less than atmospheric at a temperature of 250 F.

' BERT H. LINCOLN. 1 GORDON D. BYRKIT.

Patent 1'10. 2,261 5l9.

CERTIFICATE OF CORRECTION.

' December 2, 1941.

BERT H, LINCOLN, ET AL.

- It is hereby certified that-error appears in the printed specification of the'above numbered patent requiring correction as follows: Page 5, sec-f 0nd colunin, line 51;, claim 9, after the word "organic" second occurrence,

insert --oxy gen-- and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case "in the lfat'ent Office.

Signed and sealed this 13th Clar of January, A. D. 1,914.2,

Henry Van Arsdale, V (Seal) Acting Commissioner of Patents. 

